TW200916573A - Composition for cleaning anticorrosion and method for producing semiconductor or displayer device - Google Patents

Composition for cleaning anticorrosion and method for producing semiconductor or displayer device Download PDF

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Publication number
TW200916573A
TW200916573A TW097126613A TW97126613A TW200916573A TW 200916573 A TW200916573 A TW 200916573A TW 097126613 A TW097126613 A TW 097126613A TW 97126613 A TW97126613 A TW 97126613A TW 200916573 A TW200916573 A TW 200916573A
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Taiwan
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acid
cleaning
copper
corrosion
wiring
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TW097126613A
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Chinese (zh)
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TWI458822B (en
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Kenji Shimada
Hiroshi Matsunaga
Kojiro Abe
Kenji Yamada
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Mitsubishi Gas Chemical Co
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/10—Other heavy metals
    • C23G1/103—Other heavy metals copper or alloys of copper
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0073—Anticorrosion compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/28—Heterocyclic compounds containing nitrogen in the ring
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/33—Amino carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/02—Inorganic compounds
    • C11D7/04—Water-soluble compounds
    • C11D7/10—Salts
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/26—Organic compounds containing oxygen
    • C11D7/265—Carboxylic acids or salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/32—Organic compounds containing nitrogen
    • C11D7/3209—Amines or imines with one to four nitrogen atoms; Quaternized amines
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/32—Organic compounds containing nitrogen
    • C11D7/3245—Aminoacids
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/32—Organic compounds containing nitrogen
    • C11D7/3263—Amides or imides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/32—Organic compounds containing nitrogen
    • C11D7/3281—Heterocyclic compounds
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/04—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors
    • C23G1/06—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02041—Cleaning
    • H01L21/02057—Cleaning during device manufacture
    • H01L21/0206—Cleaning during device manufacture during, before or after processing of insulating layers
    • H01L21/02063—Cleaning during device manufacture during, before or after processing of insulating layers the processing being the formation of vias or contact holes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02041—Cleaning
    • H01L21/02057—Cleaning during device manufacture
    • H01L21/02068—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces
    • C11D2111/22—Electronic devices, e.g. PCBs or semiconductors

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Wood Science & Technology (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Computer Hardware Design (AREA)
  • Power Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Emergency Medicine (AREA)
  • Health & Medical Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Cleaning Or Drying Semiconductors (AREA)
  • Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)
  • Detergent Compositions (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)

Abstract

Provided is a composition for cleaning anticorrosion which is used in the procedure of semiconductor device etc. comprising metal wiring with copper, wherein the contents of the anticorrosive agent is anyone of pyrazole derivative consisting of pyrazole, 3, 5-dimethylpyrazole; triazole derivative consisting of 1, 2, 4-triazole; amino carboxylates consisting of iminodiacetate, ethylenediamine dipropionate; and disulfide compound consisting of di-isopropyl disulfide, diethyl disulfide. The contents of the cleaning agent is anyone of ammonium fluoride, tetramethyl ammonium fluoride, ammonium acetate, acetic acid, glyoxalic acid, oxalic acid, ascorbic acid, 1, 2-diaminopropane and dimethyl acetoamide. Furthermore, provided is a method for producing semiconductor element etc. form by using the said composition cleaning anticorrosion.

Description

200916573 九、發明說明： 【發明所屬之技術領域】 本發明係有關於一種洗淨防蝕用 防蝕用組成物而成的半導體元件或顯 淨防触用組成物在顯示元件或顯示元 被處理物表面的蝕刻殘渣，防止含銅 產生變質，且能夠容易地除去在成膜 配線上的防蝕劑。 【先前技術】 高積體化而成的LSI等的半導體 係使用微影法。藉由該微影法來製造 應用下述一系列的製程。首先，在矽 矽氧化膜等的層間絕緣膜，其目的係 之金屬膜等的導電薄膜或配線間的絕 均勻地塗布光阻劑來設置感光層，並 光及顯像處理來形成需要的光阻圖案 阻圖案作爲遮罩而選擇性地對下層部 ，在該薄膜形成需要的配線圖案。然 程用以完全除去光阻圖案。 近年來，半導體元件之高積體化 亦必須逐漸微細化。伴隨著，在上述 式蝕刻法逐漸成爲主流。在乾式蝕刻 的圖案周邊部，會產生起因於乾式蝕 加工膜乾式蝕刻裝置內的處理室構f 組成物及使用該洗淨 示元件之製法，該洗 件之製程，能夠除去 或銅合金的金屬配線 製程之前黏附在金屬 元件之製造方法通常 半導體元件時通常是 晶圓等的基板上形成 進行導電用配線材料 緣。隨後，在其表面 對其選擇性地施行_ 。接著，藉由將該光 的薄膜施行蝕刻處_ 後，採用一系列的製 進展，圖案加工尺寸 選擇性蝕刻處理，車纟 處理，已知在所形1¾ 刻氣體、光阻劑、被 ;等之殘渣（以下稱爲 200916573 「蝕刻殘渣」）。該蝕刻殘渣特別是殘留於通孔內部及其周 邊部時，會導致高電阻化、或產生電短路等不良的情況。 因爲此種電路的微細化進展，以往大量使用作爲配線 材料之以鋁爲主成分的材料，因爲電阻高，難以使電路以 指定的速度動作。因而’逐漸增加利用電阻比鋁低且遷移 特性優良之銅。 但是’銅若連接絕緣材料時，擴散至絕緣材料致使其 絕緣性降低。因此，必須設置用以防止銅的擴散之膜（以下 ’稱爲「防止擴散膜」）。若除去蝕刻殘渣時，因爲銅配線 的一部分露出’在隨後的製程必須形成上述防止擴散膜。 但是，除去蝕刻殘渣而銅露出時，因爲銅非常容易變質， 所以在被防止擴散膜保護之前會產生腐蝕刻或氧化等。具 體例係如下舉出。 通常，在剛洗淨後，有使用有機溶劑或超純水來沖洗 洗淨液之製程，但是洗淨液容易吸收大氣中的二氧化碳而 呈弱酸性。使用該弱酸性的水洗淨銅時，可觀察到銅腐蝕 。又，將銅放置在大氣中時，因大氣中的氧之作用，表面 會被氧化。因爲此種已變質的銅之電阻上升或與防止擴散 膜之黏附力降低，變質腐蝕時會導致產生空隙。近年來， 由於微細化逐漸進展，即便以往被容許之稍微變質，亦會 對半導體元件產生重大的影響而成爲不良的原因。考慮黏 附防蝕劑用以防止露出的銅產生變質，作爲防止此種不良 之方法。 在堆積防止擴散膜之製程’對防止銅表面的腐蝕之有 200916573 效的防蝕劑係與變質的銅同樣地會成爲電阻上升或成爲與 防止擴散膜的黏附性降低、產生空隙之原因。因此，必須 將黏附的防鈾劑確實地除去至實用上沒有問題的程度，但 是防蝕劑的除去並不容易。又，因爲從銅表面除去防蝕劑 後至堆積防止擴散膜，若銅長時間露出在大氣中時會產生 變質，若未在即將堆積防止擴散膜之前除去防蝕劑時沒有 效果。 如此，爲了得到高精確度、高品質的半導體元件，在 剛使用洗淨液除去蝕刻殘渣後至即將於表面堆積防止擴散 膜之前’抑制包含腐蝕之銅的變質，在形成防止擴散膜之 製程使潔淨的表面露出係非常重要的。因此，要求一種兼 具洗淨與防蝕之洗淨液，其具有除去蝕刻殘渣的能力，且 在剛除去蝕刻殘渣後至即將於表面堆積防止擴散膜之前能 夠抑制銅的變質，進而在堆積防止擴散膜時能夠供潔淨的 銅表面。 對應銅配線之洗淨液，先前有提案揭示一種洗淨液（ 特開2002-2895 69號公報），其係由氟化銨、極性有機溶劑 、水及環氧聚醯胺所構成。但是該技術即便能夠防止洗淨 中的變質’但是無法防止洗淨後的變質。亦即，無法防止 前述銅配線的變質。 含有對應銅配線的防蝕劑之洗淨液，有提案揭不一種 洗淨液（特表2005-502734號公報），其係含有1,3-二羰基化 合物作爲防蝕劑。但是，該洗淨液在剛洗淨後必須有使用 超純水或有機溶劑沖洗之製程，此時防蝕劑亦被除去。因 200916573 此，無法防止洗淨後的腐蝕。 此等技術以外，含有對應銅配線的防蝕劑之洗 有提案（特開200 1 -22096號公報、特開2003 - 3 5 963 '特開2003- 1 67360號公報）揭示含有苯并三唑化合 烯基羧酸或還原劑做爲防蝕劑之洗淨液。如前述， 係在剛除去蝕刻殘渣後至即將堆積防止擴散膜之前 配線’只有在即將堆積防止擴散膜之前完全地被脫 能夠得到防止銅配線變質之效果。亦即，使用防蝕 僅是洗淨中的防蝕，且若沒有在適當的時序進行除 劑則不能得到高品質的半導體元件。該等前述技術 去防蝕劑之方法完全沒有任何揭示或暗示。 在特開2002-975 84號公報，記載一種洗淨液作 體晶圓上的銅配線之防蝕劑，該洗淨液係添加具有 菸鹼酸等含有氮原子的六員環之雜環化合物而成。 劑未被除去，或是在該銅配線上製造矽氮化膜時被 但是關於從洗淨後至製造矽氮化膜所產生的銅配線 ，完全沒有任何揭示或暗示。 在特開200 1 -27923 1號公報，提案揭示一種銅 防蝕劑，其係含有聯二吡啶、雙酚、乙烯基吡啶、 、7 -羥基-5 -甲基 1，3，4 -三氮吲哚阱、2 -胺基-1，3，4 -噻 具有雜五員環的化合物之液體。但是，該技術係硏 之技術，其目的並非從除去殘渣製程至即將堆積防 膜之前抑制銅配線的腐蝕。 在特開2000-282096號公報、特開2005-333104 淨液， 號公報 物、乙 防蝕劑 保護銅 離時才 劑時不 去防蝕 對於除 爲半導 嘌呤、 該防蝕 除去， 之防鈾 配線的 柳醛肟 二唑等 磨製程 止擴散 號公報 200916573 ’揭示一種含有咪唑類、噻唑類及三唑類作爲防蝕劑之洗 淨液’但是未揭示關於防蝕劑之除去方法。 由上述’得知強烈希望有一種洗淨液，從除去殘渣製 程至即將在銅配線的表面堆積防止擴散膜之前能夠抑制銅 配線的腐蝕’且在堆積防止擴散膜時能夠容易地除去防蝕 劑成分，來提供潔淨的銅表面。 【發明内容】 發明所欲解決之課題 本發明係提供一種洗淨防蝕用組成物，在具有含銅金 屬配線之半導體元件或顯示元件之製程，其能夠發揮能夠 除去在蝕刻處理後堅固地黏附被處理物表面之蝕刻殘渣且 不會對半導體元件或顯示元件造成損傷之「洗淨性」；防 止所得到潔淨的金屬配線受到腐蝕之「防蝕性」；及在即 將使用防止擴散膜覆蓋金屬配線之前能夠藉由規定的處理 將防蝕成分容易地從金屬配線除去之「易除去性」。 又，提供一種半導體元件或顯示元件之製法，使用該 洗淨防蝕用組成物能夠邊洗淨除去蝕刻殘渣防止含銅金屬 配線的變質。 解決課題之手段 爲了解決上述課題’本發明者等進行檢討各種洗淨成 分及防蝕劑成分時，發現特定的吡唑衍生物、三唑衍生物 、胺基羧酸類及二硫醚化合物之任一者的防蝕劑與特定洗 淨劑之組合，能夠滿足上述「洗淨性」、「防蝕性」及「 易除去性」，而完成了本發明。 200916573 亦即，本發明係如下述。 一種洗淨防蝕用組成物，其係使用於具有含銅金屬配 線之半導體元件或顯示元件等的製程，含有防蝕劑成分及 洗淨劑成分， 前述防蝕劑成分係選自由吡唑、3,5 -二甲基吡唑、3,5-吡唑二羧酸一水合物、吡唑-1·甲脒鹽酸鹽、3 -胺基-5 -羥基 吡唑、1-苯基吡唑、3-胺基-4-苯基吡唑、1,2,4-三唑、4-胺 基-3,5-二甲基-1,2,4-三唑、亞胺基二乙酸、羥基伸乙二胺 三乙酸、乙二醇醚二胺四乙酸、羥乙基亞胺基二乙酸、三 伸乙四胺六乙酸、伸乙二胺二丙酸鹽酸鹽、二異丙基二硫 醚、二丁基二硫醚及二乙基二硫醚所組成群組之至少1種 ，而 前述洗淨劑成分係選自由氟化銨、氟化四甲銨、乙酸 銨、乙酸、乙醛酸、草酸、抗壞血酸、1,2 -二胺基丙烷及二 甲基乙醯胺所組成群組之至少1種。 又，係一種半導體元件或顯示元件之製法，包含以下 製程： 配線圖案形成製程，其係在基板上依照順序形成作爲 導電用配線使用之含銅的導電薄膜及用以進行配線間的絕 緣之層間絕緣膜，並在該表面塗布光阻劑來形成感光層且 對其施行選擇性曝光及顯像處理來形成光阻圖案，並且以 該光阻圖案作爲遮罩而施行蝕刻處理後’藉由灰化除去光 阻劑來形成配線圖案； 洗淨處理製程，其係藉由洗淨處理來除去蝕刻處理後 -10- 200916573 的蝕刻殘渣； 加熱處理製程，其係在前述洗淨處理製程後施行加熱 處理；及 防止擴散膜形成製程，其係在藉由前述加熱處理而露 出的配線圖案表面形成防止擴散膜； 前述洗淨處理製程之洗淨處理係使用如申請專利範圍 第1項之洗淨防蝕用組成物，且 前述加熱處理製程之加熱處理的條件係壓力爲 0.001~600Pa、溫度爲 100°C 〜300°C。 【實施方式】 實施發明之最佳形態 [1.洗淨防蝕用組成物] 本發明的洗淨防蝕用組成物係含有規定的防融劑成分 與規定的洗淨劑成分。以下，係就此等來加以說明。 (防鈾劑成分） 本發明之防蝕劑成分係與洗淨劑成分一同混合，所以 不可阻礙洗淨，且爲了確保潔淨的金屬配線表面，必須藉 由規定的處理（減壓加熱）來完全地除去。防蝕劑成分若不 只是黏附金屬配線而且亦黏附洗淨對象之一的金屬配線氧 化物時，無法得到充分的洗淨能力。因此，選擇能夠選擇 性地黏附於清淨的金屬配線之防蝕劑成分係必要的。又， 防餽劑成分若與金屬配線堅強地結合時，難以藉由減壓加 熱來從金屬配線表面除去。因此，選擇具有以適當力量黏 附的性質之防蝕劑成分係必要的。 -11 - 200916573 本發明所使用的防蝕劑成分（防蝕劑），首先可舉出具 有含有2或3個氮原子的雜環且其氮的至少2個彳系彳目鄰之 化合物或其衍生物，具體上係使用吡唑或特定的眼^坐衍生 物或1，2,3-三唑衍生物、1,2,4-三唑衍生物等特定的三哩衍 生物。或是使用特定的胺基聚羧酸類、特定的二硫醚化合 物。該等防蝕劑成分可單獨使用，或組合使用2種以上。 洗淨防蝕用組成物中的防蝕劑成分之濃度係以 0.001 ~5質量％爲佳，以0.005-3質量％爲更佳。防蝕劑成分 的濃度爲0.00 1質量％以上時，能夠使銅配線的防蝕效果充 分，爲5質量％以下時，能夠謀求防蝕效果與經濟性的平衡。 吡唑或特定的吡唑衍生物或特定的三唑衍生物係使用 吡唑、吡唑-1 -甲脒鹽酸鹽、3，5 -二甲基吡唑、3，5 -吡唑二羧 酸一水合物、3 -胺基-5-羥基吡唑' 1-苯基吡唑、3 -胺基- 4-苯基吡唑、1，2,3-三唑、1，2,4-三唑、3-胺基-1,2,4-三唑、4-胺基-1，2,4-三唑及4·胺基-3,5-二甲基-i，2,4-三唑之任一種。 此等之中，較佳是吡唑-1 -甲眯鹽酸鹽、3 , 5 -二甲基吡 唑、3,5-吡唑二羧酸一水合物、3-胺基-5-羥基吡唑、1-苯基 吡唑、3-胺基-4-苯基吡唑、1,2,4-三唑及4-胺基-3,5-二甲基 -1,2,4 -三嗖。又，最佳是3,5 -二甲基n比哩。 特定的胺基聚羧酸類係使用伸乙二胺四羧酸、羥基伸 乙二胺三乙酸、乙二醇醚二胺四乙酸、亞胺二乙酸、羥乙 基亞胺二乙酸、三伸乙四胺六乙酸、二胺基環己烷四乙酸、 二伸乙三胺五乙酸及伸乙二胺二丙酸鹽之任一種。此等之 中’較佳是亞胺二乙酸、羥基伸乙二胺三乙酸、乙二醇醚 -12- 200916573 二胺四乙酸、羥乙基亞胺二乙酸、三伸乙四胺六乙酸及伸 乙二胺二丙酸鹽，特佳是亞胺基二乙酸、羥基伸乙二胺三 乙酸、乙二醇醚二胺四乙酸、三伸乙四胺六乙酸及伸乙二 胺二丙酸鹽。 特定的二硫醚化合物係使用二乙基二硫醚、二異丙基 一硫魅、—丁基一硫醚之任一種。其中較佳是二乙基二硫 魅及一異丙基一硫酸’特佳是一乙基二硫酸。 以對清淨的金屬配線具選擇性且以適當力量黏附之方 式來選擇防蝕劑成分係必要的。通常氮、氧、硫係容易與 銅形成錯合物。推測上述化合物係與銅形成錯合物來顯示 防蝕效果。又，推測藉由立體障礙或電子密度能夠抑制成 爲適當的結合力。上述的防蝕劑成分係例如使用在2〇〇它左 右可脫離者爲佳。 本發明之防蝕劑能夠以將上述特定的防蝕劑成分混合 R水溶液或水溶液有機溶劑而成的狀態來添加於後述的洗 淨劑成分中。 水溶性有機溶劑可例示Ν,Ν-二甲基甲醯胺、二甲基亞 颯、甲基-2_吡咯啶酮、7 -丁內酯及乙二醇一甲基醚等， 但是未限定於此等。 (洗淨劑成分） '冼淨劑成分（洗淨劑）係使用氟化銨、氟化四甲銨、乙 酸鏡、乙酸、乙醛酸、草酸、抗壞血酸、1，2 -二胺基丙烷及 二甲基乙醯胺之任一者。其中，較佳是氟化銨、氟化四甲 錢、乙酸銨、乙酸、及1，2·二胺基丙烷。 -13- 200916573 洗淨防蝕用組成物中的洗淨劑成分的濃度以〇 . 〇卜90 質量％爲佳，以0.0 3〜8 6質量％爲更佳。濃度爲0.0 1質量％ 以上時，能夠使洗淨效果充分，90質量％以下時’能夠謀 求洗淨效果與經濟性之平衡。 本發明的洗淨防蝕用組成物能夠藉由混合上述特定的 防蝕劑成分及洗淨劑成分（各自的成分亦可以混合在特定 的溶劑中）而得到。又，洗淨防蝕用組成物在不損害本發明 的目的之範圍，亦可以調配以往使用作爲洗淨液之添加劑。 本發明的洗淨防蝕用組成物能夠應用的半導體元件及 顯示元件若是配線材料係以Cu作爲主成分時沒有特別限 定。可舉出例如矽、非晶質矽、多晶矽、玻璃等的基板材 料；氧化矽、氮化矽、碳化矽及該等的衍生物等的絕緣材 料；鈦、氮化鈦、鉬、氮化鉬及該等的衍生物等的阻障材 料；含有以銅爲主成分且含鎢、鈦-鎢、鋁、鋁合金、鉻、 鉻合金等的配線材料之半導體元件及顯示元件、或鎵-砷、 鎵-磷、銦-磷等的化合物半導體、或鉻氧化物等的氧化物 半導體等。 [2.半導體元件或顯示元件的製法] 本發明的半導體元件或顯示元件的製法，包含以下製 程：配線圖案形成製程，其係在基板上依照順序形成作爲 導電用配線使用之含銅的導電薄膜及用以進行配線間的絕 緣之層間絕緣膜，並在該表面塗布光阻劑來形成感光層且 對其施行選擇性曝光及顯像處理來形成光阻圖案，並且以 該光阻圖案作爲遮罩而施行蝕刻處理後，藉由灰化除去光 -14- 200916573 阻劑來形成配線圖案；洗淨處理製程，其係藉由洗淨處理 來除去触刻處理後的蝕刻殘渣；加熱處理製程，其係在前 述洗淨處理製程後施行加熱處理；及防止擴散膜形成製 程，其係在藉由前述加熱處理而露出的配線圖案表面形成 防止擴散膜； 在洗淨處理製程之洗淨處理係使用本發明的洗淨防蝕 用組成物。 洗淨處理的溫度以在20〜50 °C的範圍爲佳，可按照擇鈾 刻條件或所使用半導體基體而適當地選擇。 洗淨處理能夠按照必要並用超音波。藉由洗淨處理除 去半導體基體上的蝕刻殘渣後之沖洗液，不必使用如醇之 有機溶劑而只要使用水沖洗即充分。洗淨處理後，因爲配 線圖案的露出部分防蝕劑係以適當的黏附力（能夠藉由後 述的加熱處理而除去的程度之黏附力）覆蓋，即便隨後長期 間保存亦能夠繼續顯現防蝕效果。 在加熱處理製程之加熱處理時，在藉由後述的防止擴 散膜形成製程形成防止擴散膜之前，必須使防蝕劑成分脫 離至實用上無問題之程度。因此，加熱處理時設定規定減 壓度係必要的’該壓力爲0.001 ~600Pa。進行脫離時之壓力 大於600Pa時，防蝕劑成分未被除去至實用上無問題之程 度而殘留於銅表面。又，應用大於600Pa時而完全脫離之 化合物作爲本發明的目的之防蝕劑成分時，即便在2 5。(：左 右的條件’會有一部分防蝕劑產生脫離致使防蝕效果不充 分的情形。從實用上的觀點，進行脫離時之壓力下限爲 -15- 200916573 O.OOlPa ° 在上述記載之減壓下’爲了使本發明的防蝕劑成分脫 離至實用上無問題之程度之溫度（加熱處理溫度）爲loot ~ 300°C，以 120°C 〜2 80 °C 爲佳，以 150°C 〜250°C 爲更佳。 在溫度小於1〇〇°C而完全脫離時，即便25 °C左右的條 件’會有一部分防鈾劑產生脫離致使防蝕效果不充分的情 形。必須大於3 0 0 °C才會脫離時，在脫離防蝕劑之製程時會 造成損傷。 又’在上述配線圖案形成製程所應用之各層的形成條 件或材料、触刻條件等能夠應用先前通常已知的技術。又， 在防止擴散膜形成製程之防止擴散膜的材料或形成方法亦 能夠應用先前通常已知的技術。 接著，藉由實施例及比較例更具體地說明本發明。但 是’本發明完全未限定於此等實施例。 (半導體元件的製造） 如下進行，來製造半導體元件。 首先’如第1圖所不，在銅配線之導電薄膜1上藉由 CVD法依照順序堆積碳化矽膜2及層間絕緣膜之LoW-k膜 3。隨後’塗布光阻劑並使用通常的光學技術加工光阻劑。 使用乾式蝕刻技術將Low-k膜3及碳化矽膜2蝕刻加工成 需要的圖案並形成通孔，且藉由灰化除去光阻劑，來製造 半導體元件。在製造後的半導體元件之通孔內壁係黏附者 蝕刻殘渣4。 [實施例1 ~ 2 0及比較例1〜2 0 ] -16- 200916573 在下述洗淨劑成分混合下述表1及表2所示之 成分，來製造實施例1〜20及比較例1〜20的洗淨防 成物。使用該等的洗淨防蝕用組成物來進行下述評{ (洗淨劑成分） Α液：0.4質量％氟化銨、0.03質量％乙醛酸、剩餘 水 B液：12質量％乙酸、15.2質量％乙酸銨、57.5質量 基乙醯胺、1質量％氟化銨、剩餘部分爲水 C液：3.4質量％草酸、0.05質量％抗壞血酸、剩餘 水 D液：0.1質量％1,2-二胺基丙烷、0.5質量％氟化四 1 . 5質量％乙酸、剩餘部分爲水 (評價1 :洗淨性） 將如第1圖所示之半導體元件浸漬在各洗淨防 成物，於2 5 °C浸漬2分鐘後，使用超純水沖洗並乾 過上述製程後，使用掃描型電子顯微鏡（SEM HIGHTECHNOLOGIES公司製S-5 500)觀察表面狀態， 係評價蝕刻殘渣的除去性、銅配線體的腐蝕及Low. 的損傷。 (評價2 :防蝕性） 爲了確認防蝕劑的防蝕能力，將全面鍍敷銅膜 的矽晶圓，在各洗淨防蝕用組成物中於 2 5 °C浸漬 後，使用超純水沖洗並乾燥。隨後，將該矽晶圓於 漬於熔解二氧化碳而成的超純水（比電阻爲0.2 Μ Ω 防蝕劑 飽用組 賈。 部分爲 %二甲 部分爲 甲銨、 蝕用組 燥。經 、日立 洗淨性 -k材料 而形成 2分鐘 25°C 浸 -17- 200916573 以下稱爲碳酸水）5分鐘。使用SEM觀察所得到的銅表面， 來判斷銅的腐蝕。認爲銅腐蝕者係防蝕劑未具有功能。 (評價3 :防蝕性） 爲了確認防蝕劑之抑制銅變質的能力，將全面鍍敷銅 膜而形成的矽晶圓，在各洗淨防蝕用組成物中於25 °C浸漬 2分鐘後，使用超純水沖洗並乾燥。隨後，在2 2 °C、濕度 45 %的潔淨室內放置3天後，使用X射線光電子分光裝置 (XPS、VG Scientific公司製）測定銅的狀態。 (評價4 :易除去性） 爲了確認從防蝕劑成分的銅表面之脫離性（除去性）而 進行下述實驗。首先，將全面鍍敷銅膜而形成的矽晶圓， 在25 °C浸漬於下述表1 ~表3所示洗淨防蝕用組成物中在評 價2觀察到具有效果者2分鐘後，使用超純水沖洗並乾燥。 將該銅膜於0.1 Pa的減壓下、200 °C加熱5分鐘。隨後，於 25 °C浸漬在碳酸水5分鐘並使用SEM觀察銅表面。在評價 2觀察到具有效果之洗淨防蝕用組成物，在銅表面係形成 用以防止受到碳酸水腐蝕之膜。藉由減壓加熱黏附有保護 膜之銅膜將保護膜從銅表面除去時，接著浸漬在碳酸水 時，應該能夠觀察到在銅表面產生腐蝕。因此，雖然在評 價2使用 SEM觀察時無法觀察到銅產生腐蝕係良好的結 果，但是在評價4使用SEM觀察時，能夠觀察到銅產生腐 蝕係良好的結果 -18- 200916573 [表1] 實 施 例 洗 淨 液 防蝕劑 評價1 評 價 2 評 價 3 評 價 4 mm 濃度 軍暈 % 蝕刻 殘渣 除去性 銅的 防蝕性 Low-k 材料的 損傷 1 A 1，2,4-三唑 0.01 ◎ ◎ ◎ ◎ ◎ ◎ 2 B 1，2,4-三唑 0.01 ◎ ◎ ◎ ◎ ◎ ◎ 3 C 1，2,4-三唑 0.01 ◎ ◎ ◎ ◎ ◎ ◎ 4 A 亞胺二乙酸 1 ◎ ◎ ◎ ◎ ◎ ◎ 5 A 二乙基二硫醚 0.1 ◎ ◎ ◎ ◎ ◎ ◎ 6 D 吡唑 0.01 ◎ ◎ ◎ ◎ ◎ 〇 7 D 3,5-二甲基吡唑 0.01 ◎ ◎ ◎ ◎ ◎ ◎ 8 B 3,5-二甲基吡唑二 羧酸一水合物 0.01 ◎ ◎ ◎ 〇 〇 ◎ 9 D 羥基伸乙二胺三 乙酸 0.01 ◎ ◎ ◎ 〇 〇 〇 10 A 吡哩-1-甲脒鹽酸 鹽 0.01 ◎ ◎ ◎ ◎ ◎ 〇 11 B 3-胺基-5-羥基吡 唑 0.01 ◎ ◎ ◎ ◎ ◎ 〇 12 C 1-苯基吡唑 0.01 ◎ ◎ ◎ ◎ ◎ 〇 13 D 3-胺基-4-苯基吡 唑 0.01 ◎ ◎ ◎ ◎ ◎ 〇 14 A 4-胺基-3,5-二甲基 -1,2,4-三唑 0.01 ◎ ◎ ◎ ◎ ◎ 〇 15 C 乙二醇醚二胺四 乙酸 0.01 〇 〇 〇 〇 〇 〇 16 D 羥乙基亞胺基二 乙酸 0.01 〇 〇 ◎ 〇 〇 〇 17 A 三伸乙四胺六乙 酸 0.01 ◎ ◎ ◎ 〇 〇 〇 18 A 伸乙二胺二丙酸 鹽酸鹽 0.01 ◎ ◎ ◎ ◎ ◎ ◎ 19 B 二異丙基二硫醚 0.01 ◎ ◎ ◎ ◎ ◎ ◎ 20 C 二丁基二硫醚 0.01 ◎ ◎ ◎ 〇 〇 〇 -19- 200916573 [表2][Technical Field] The present invention relates to a semiconductor element or a clean anti-touch composition which is a composition for cleaning an anti-corrosion for anti-corrosion on the surface of a display element or a display object The etching residue prevents deterioration of the copper-containing material, and the corrosion inhibitor on the film formation wiring can be easily removed. [Prior Art] A semiconductor such as LSI which is highly integrated is a lithography method. The following series of processes are applied by the lithography method. First, in an interlayer insulating film such as a tantalum oxide film, a photoresist is uniformly applied between a conductive film or a wiring such as a metal film for the purpose of providing a photosensitive layer, and light and development processing are performed to form a desired light. The resist pattern pattern is selectively applied to the lower layer portion as a mask, and a desired wiring pattern is formed on the film. It is used to completely remove the photoresist pattern. In recent years, the high integration of semiconductor components has to be gradually miniaturized. Along with this, the above etching method has gradually become mainstream. In the peripheral portion of the dry etching pattern, a composition of the processing chamber structure in the dry etching film dry etching apparatus and a manufacturing method using the cleaning element are produced, and the processing of the cleaning member can remove the metal of the copper alloy. In the method of manufacturing a metal element before the wiring process, a semiconductor element is usually formed on a substrate such as a wafer to form a conductive wiring material. Subsequently, _ is selectively applied to the surface thereof. Then, after the film of the light is etched, a series of progress is made, the pattern is processed by a size selective etching process, and the rutting process is known to be in the form of a gas, a photoresist, a quilt, etc. Residue (hereinafter referred to as 200916573 "etching residue"). When the etching residue remains in the inside of the through hole and its peripheral portion, the etching residue may cause an increase in resistance or an electrical short circuit. In order to advance the miniaturization of such a circuit, a material mainly composed of aluminum as a wiring material has been conventionally used, and since the electric resistance is high, it is difficult to operate the circuit at a predetermined speed. Therefore, copper which is lower in resistance than aluminum and excellent in migration characteristics is gradually increased. However, when copper is connected to an insulating material, it diffuses to the insulating material to lower its insulation. Therefore, it is necessary to provide a film for preventing the diffusion of copper (hereinafter referred to as "preventing diffusion film"). When the etching residue is removed, since a part of the copper wiring is exposed, the above-described diffusion preventing film must be formed in a subsequent process. However, when the etching residue is removed and the copper is exposed, since copper is easily deteriorated, corrosion etching, oxidation, or the like may occur before being protected by the diffusion preventing film. The specific examples are as follows. Usually, after washing, there is a process of washing the washing liquid with an organic solvent or ultrapure water, but the washing liquid easily absorbs carbon dioxide in the atmosphere and is weakly acidic. When the copper was washed with the weakly acidic water, copper corrosion was observed. Also, when copper is placed in the atmosphere, the surface is oxidized by the action of oxygen in the atmosphere. Since the resistance of such deteriorated copper rises or the adhesion to the diffusion preventing film is lowered, voids are caused by deterioration. In recent years, as the miniaturization progresses, even if it is allowed to deteriorate slightly in the past, it will have a significant influence on the semiconductor element and become a cause of failure. Adhesion inhibitors are considered to prevent deterioration of exposed copper as a means of preventing such defects. In the process of depositing the diffusion preventing film, the anticorrosive agent of the effect of preventing corrosion of the copper surface has the same resistance as that of the deteriorated copper, and the adhesion to the diffusion preventing film is lowered to cause voids. Therefore, it is necessary to surely remove the adhered uranium preventive agent to the extent that it is practically not problematic, but the removal of the corrosion inhibitor is not easy. Further, since the anti-corrosion agent is removed from the copper surface to the deposition preventing diffusion film, if the copper is exposed to the atmosphere for a long time, it is deteriorated, and if the anti-corrosion agent is not removed immediately before the diffusion preventing film is deposited, there is no effect. In order to obtain a high-precision, high-quality semiconductor element, the deterioration of the copper containing the etching is suppressed immediately after the etching residue is removed by using the cleaning liquid until the diffusion film is deposited on the surface, and the process for preventing the diffusion film is formed. A clean surface is very important. Therefore, there is a demand for a cleaning solution which has both cleaning and anti-corrosion, which has the ability to remove etching residues, and can suppress deterioration of copper immediately after removal of the etching residue, immediately before deposition of the diffusion preventing film on the surface, and further prevent deposition from spreading. A clean copper surface is available for the film. In the case of the cleaning solution for the copper wiring, a cleaning liquid (Japanese Unexamined Patent Publication No. 2002-2895-69), which is composed of ammonium fluoride, a polar organic solvent, water, and an epoxy polyamine. However, this technique can prevent deterioration after washing, but it cannot prevent deterioration after washing. That is, deterioration of the aforementioned copper wiring cannot be prevented. There is a proposal to disclose a cleaning solution containing an anticorrosive agent for a copper wiring, which is a cleaning solution (Japanese Laid-Open Patent Publication No. 2005-502734), which contains a 1,3-dicarbonyl compound as an anticorrosive agent. However, the cleaning solution must be washed with ultrapure water or an organic solvent immediately after washing, and the corrosion inhibitor is also removed. As of 200916573, corrosion after washing cannot be prevented. In addition to these technologies, there is a proposal to wash a corrosion inhibitor containing a copper wire (Japanese Unexamined Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. The alkenyl carboxylic acid or reducing agent acts as a cleaning solution for the corrosion inhibitor. As described above, immediately after the etching residue is removed until the diffusion preventing film is deposited, the wiring ′ is completely removed before the diffusion preventing film is deposited. The effect of preventing deterioration of the copper wiring can be obtained. That is, the use of corrosion is only an anti-corrosion in the cleaning, and a high-quality semiconductor element cannot be obtained unless the removal agent is performed at an appropriate timing. The foregoing techniques for removing corrosion inhibitors are not disclosed or implied at all. JP-A-2002-97584 discloses an anticorrosive agent for a copper wiring on a cleaning liquid wafer, which is a heterocyclic compound having a six-membered ring containing a nitrogen atom such as nicotinic acid. to make. The agent was not removed, or when the tantalum nitride film was formed on the copper wiring, but there was no disclosure or suggestion about the copper wiring generated from the cleaning to the production of the tantalum nitride film. In JP-A No. 2001-27923, the proposal discloses a copper corrosion inhibitor containing bipyridine, bisphenol, vinyl pyridine, 7-hydroxy-5-methyl 1,3,4-triazaindene. A helium trap, a 2-amino-1,3,4-thiatium compound having a heterocyclic ring of a compound. However, this technique is not intended to suppress corrosion of copper wiring from the removal of the residue process until the film is deposited. In the case of JP-A-2000-282096, JP-A-2005-333104, No. 2005-333104, and B-protection agent to protect the copper from the time of the agent, the anti-corrosion is removed, and the anti-uranium wiring is removed. Resveratrol Dispersion No. 200916573 'Disinfecting a cleaning solution containing an imidazole, a thiazole, and a triazole as an anticorrosive agent' but does not disclose a method for removing the anticorrosive agent. From the above, it is known that it is strongly desired to have a cleaning liquid, and it is possible to suppress the corrosion of the copper wiring from the removal of the residue process until the deposition of the diffusion preventing film on the surface of the copper wiring, and the corrosion inhibitor component can be easily removed when the diffusion preventing film is deposited. To provide a clean copper surface. DISCLOSURE OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION The present invention provides a cleaning anticorrosive composition capable of exhibiting a process of removing a semiconductor element or a display element having a copper-containing metal wiring, which is capable of removing a strong adhesion after etching treatment. The "cleaning property" of the etching residue on the surface of the object without causing damage to the semiconductor element or the display element; the "corrosion resistance" of preventing the cleaned metal wiring from being corroded; and the use of the diffusion preventing film to cover the metal wiring immediately before use The "easy-removability" in which the corrosion-resistant component can be easily removed from the metal wiring by a predetermined process. Further, a method for producing a semiconductor element or a display element can be provided, and the composition for cleaning and etching can be removed by removing the etching residue to prevent deterioration of the copper-containing metal wiring. In order to solve the above problems, the inventors of the present invention have found any of a specific pyrazole derivative, a triazole derivative, an aminocarboxylic acid, and a disulfide compound when reviewing various cleaning components and corrosion inhibitor components. The combination of the corrosion inhibitor and the specific detergent can satisfy the above-mentioned "washability", "corrosion resistance" and "easy removal property", and completed the present invention. That is, the present invention is as follows. A cleaning anticorrosive composition for use in a semiconductor device or a display device having a copper-containing metal wiring, comprising a corrosion inhibitor component and a detergent component, wherein the corrosion inhibitor component is selected from pyrazole, 3, 5 - dimethylpyrazole, 3,5-pyrazoledicarboxylic acid monohydrate, pyrazole-1. formamidine hydrochloride, 3-amino-5-hydroxypyrazole, 1-phenylpyrazole, 3 -Amino-4-phenylpyrazole, 1,2,4-triazole, 4-amino-3,5-dimethyl-1,2,4-triazole, imidodiacetic acid, hydroxyl extension Ethylenediaminetriacetic acid, glycol ether diamine tetraacetic acid, hydroxyethyliminodiacetic acid, triamethylenetetramine hexaacetic acid, ethylenediamine dipropionate, diisopropyl disulfide At least one selected from the group consisting of dibutyl disulfide and diethyl disulfide, and the detergent component is selected from the group consisting of ammonium fluoride, tetramethylammonium fluoride, ammonium acetate, acetic acid, and glyoxylic acid. At least one of the group consisting of oxalic acid, ascorbic acid, 1,2-diaminopropane and dimethylacetamide. Further, a method of manufacturing a semiconductor element or a display element includes the following wiring process: a wiring pattern forming process in which a copper-containing conductive film used as a conductive wiring and an interlayer for insulating between wirings are sequentially formed on a substrate. An insulating film, and a photoresist is coated on the surface to form a photosensitive layer, and a selective exposure and development process is performed thereon to form a photoresist pattern, and the photoresist pattern is used as a mask to perform etching treatment. The photoresist is removed to form a wiring pattern; the cleaning process is performed by a cleaning process to remove the etching residue of the -10-200916573 after the etching process; and the heat treatment process is performed after the cleaning process And a diffusion preventing film forming process for forming a diffusion preventing film on a surface of the wiring pattern exposed by the heat treatment; and the cleaning process of the cleaning process is performed by using the cleaning and corrosion protection as in the first aspect of the patent application. The composition is used, and the heat treatment condition of the heat treatment process is 0.001 to 600 Pa and the temperature is 100 ° C to 300. °C. [Embodiment] The best mode for carrying out the invention [1. Composition for cleaning and anti-corrosion] The composition for cleaning and anti-corrosion of the present invention contains a predetermined anti-icing agent component and a predetermined detergent component. The following is explained in this regard. (Anti-uranium component) The corrosion inhibitor component of the present invention is mixed with the detergent component, so that it is not impeded to be cleaned, and in order to secure a clean metal wiring surface, it is necessary to completely process by a predetermined treatment (reduced pressure heating). Remove. If the corrosion inhibitor component adheres not only to the metal wiring but also to the metal wiring oxide which is one of the cleaning objects, sufficient cleaning ability cannot be obtained. Therefore, it is necessary to select an anticorrosive component that can selectively adhere to the clean metal wiring. Further, when the feedthrough component is strongly bonded to the metal wiring, it is difficult to remove it from the surface of the metal wiring by decompression heating. Therefore, it is necessary to select a corrosion inhibitor component having a property of adhering with an appropriate force. -11 - 200916573 The corrosion inhibitor component (corrosion inhibitor) used in the present invention first includes a compound having a heterocyclic ring having 2 or 3 nitrogen atoms and a nitrogen of at least two compounds of the oxime system or a derivative thereof. Specifically, a specific triterpene derivative such as pyrazole or a specific ocular derivative or a 1,2,3-triazole derivative or a 1,2,4-triazole derivative is used. Or use specific amine polycarboxylic acids, specific disulfide compounds. These corrosion inhibitor components may be used alone or in combination of two or more. The concentration of the corrosion inhibitor component in the cleaning anticorrosive composition is preferably 0.001 to 5% by mass, more preferably 0.005 to 3% by mass. When the concentration of the corrosion inhibitor component is 0.001% by mass or more, the corrosion resistance of the copper wiring can be sufficiently increased, and when it is 5% by mass or less, the balance between the corrosion prevention effect and the economy can be achieved. Pyrazole or a specific pyrazole derivative or a specific triazole derivative using pyrazole, pyrazole-1-carbamidine hydrochloride, 3,5-dimethylpyrazole, 3,5-pyrazoledicarboxylate Acid monohydrate, 3-amino-5-hydroxypyrazole ' 1-phenylpyrazole, 3-amino-4-phenylpyrazole, 1,2,3-triazole, 1,2,4- Triazole, 3-amino-1,2,4-triazole, 4-amino-1,2,4-triazole and 4·amino-3,5-dimethyl-i,2,4- Any of triazoles. Among these, pyrazole-1-carbamidine hydrochloride, 3,5-dimethylpyrazole, 3,5-pyrazoledicarboxylic acid monohydrate, 3-amino-5-hydroxyl group are preferred. Pyrazole, 1-phenylpyrazole, 3-amino-4-phenylpyrazole, 1,2,4-triazole and 4-amino-3,5-dimethyl-1,2,4- Three. Also, the best is 3,5-dimethyl n than hydrazine. Specific amine-based polycarboxylic acids are ethylenediaminetetracarboxylic acid, hydroxyethylenediaminetriacetic acid, ethylene glycol ether diaminetetraacetic acid, imine diacetic acid, hydroxyethylimine diacetic acid, and Sanshen B. Any of tetraamine hexaacetic acid, diaminocyclohexanetetraacetic acid, diethylenetriamine pentaacetic acid, and ethylenediamine dipropionate. Among these, 'imide is imine diacetic acid, hydroxyethylenediamine triacetic acid, glycol ether-12-200916573 diaminetetraacetic acid, hydroxyethylimine diacetic acid, triamethylenetetramine hexaacetic acid and Ethylenediamine dipropionate, particularly preferably iminodiacetic acid, hydroxyethylenediaminetriacetic acid, ethylene glycol ether diaminetetraacetic acid, triethylenetetramine hexaacetic acid and ethylenediamine dipropionic acid salt. As the specific disulfide compound, any of diethyl disulfide, diisopropyl monosulfide, and butyl monosulfide is used. Among them, diethyl disulfide and monoisopropyl sulfuric acid are preferred as monoethyl disulfate. It is necessary to select the corrosion inhibitor composition in a manner that is selective to the clean metal wiring harness and adhered with an appropriate force. Usually, nitrogen, oxygen, and sulfur are easily complexed with copper. It is presumed that the above compound forms a complex with copper to exhibit an anti-corrosion effect. Further, it is presumed that it is possible to suppress an appropriate bonding force by steric hindrance or electron density. The above-mentioned corrosion inhibitor component is preferably used, for example, in the case where it is detachable. The corrosion inhibitor of the present invention can be added to a detergent component to be described later in a state in which the specific corrosion inhibitor component is mixed with an aqueous solution of R or an aqueous solution of an aqueous solution. Examples of the water-soluble organic solvent include hydrazine, hydrazine-dimethylformamide, dimethyl hydrazine, methyl-2-pyrrolidone, 7-butyrolactone, and ethylene glycol monomethyl ether, but are not limited. This is the case. (Detergent component) 'The detergent component (cleaning agent) is ammonium fluoride, tetramethylammonium fluoride, acetic acid mirror, acetic acid, glyoxylic acid, oxalic acid, ascorbic acid, 1,2-diaminopropane and Any of dimethyl acetamide. Among them, preferred are ammonium fluoride, tetrafluoroanhydride, ammonium acetate, acetic acid, and 1,2·diaminopropane. -13- 200916573 The concentration of the detergent component in the composition for cleaning and anti-corrosion is preferably 90% by mass, more preferably 0.03 to 86% by mass. When the concentration is 0.01% by mass or more, the washing effect can be sufficiently obtained, and when it is 90% by mass or less, the balance between the washing effect and the economy can be achieved. The composition for cleaning and anti-corrosion of the present invention can be obtained by mixing the above-mentioned specific corrosion inhibitor component and detergent component (each component can also be mixed in a specific solvent). Further, the cleaning anticorrosive composition can also be used as an additive for the cleaning liquid in the range which does not impair the object of the present invention. The semiconductor element and the display element to which the composition for cleaning and anti-corrosion of the present invention can be applied are not particularly limited as long as the wiring material is made of Cu as a main component. Examples thereof include substrate materials such as tantalum, amorphous tantalum, polycrystalline germanium, and glass; insulating materials such as tantalum oxide, tantalum nitride, tantalum carbide, and the like; titanium, titanium nitride, molybdenum, and molybdenum nitride. And a barrier material such as a derivative thereof; a semiconductor element and a display element containing a wiring material containing copper as a main component and containing tungsten, titanium-tungsten, aluminum, an aluminum alloy, chromium, a chromium alloy, or the like, or gallium-arsenic A compound semiconductor such as gallium-phosphorus or indium-phosphorus or an oxide semiconductor such as chromium oxide. [2. Method of manufacturing semiconductor element or display element] The method of manufacturing a semiconductor element or a display element of the present invention includes the following process: a wiring pattern forming process for forming a copper-containing conductive film used as a conductive wiring on a substrate in order And an interlayer insulating film for performing insulation between the wiring lines, and coating a photoresist on the surface to form a photosensitive layer, and performing selective exposure and development processing to form a photoresist pattern, and using the photoresist pattern as a mask After the etching process is performed on the cover, the wiring pattern is formed by removing the light-14-200916573 resist by ashing; the cleaning process is performed by removing the etching residue after the etching process by the cleaning process; the heat treatment process is performed. The heat treatment is performed after the cleaning process; and the diffusion film formation process is performed, and the diffusion preventing film is formed on the surface of the wiring pattern exposed by the heat treatment; and the cleaning process is performed in the cleaning process. The composition for cleaning and anti-corrosion of the present invention. The temperature of the cleaning treatment is preferably in the range of 20 to 50 ° C, and may be appropriately selected depending on the uranium engraving conditions or the semiconductor substrate to be used. The washing process can use ultrasonic waves as necessary. The rinse liquid after removing the etching residue on the semiconductor substrate by the cleaning treatment does not have to use an organic solvent such as an alcohol, and it is sufficient to rinse with water. After the cleaning treatment, since the exposed portion of the wiring pattern is covered with an appropriate adhesion force (adhesive force to the extent that it can be removed by the heat treatment described later), the corrosion prevention effect can be continued even after long-term storage. In the heat treatment of the heat treatment process, it is necessary to remove the corrosion inhibitor component to a practical extent without any problem before the diffusion preventing film is formed by the diffusion preventing film forming process described later. Therefore, it is necessary to set a predetermined degree of depressurization during the heat treatment, which is 0.001 to 600 Pa. When the pressure at the time of the detachment is more than 600 Pa, the corrosion inhibitor component is not removed to the extent that it is practically problem-free and remains on the copper surface. Further, when a compound which is completely detached at a temperature of more than 600 Pa is used as the anticorrosive component of the object of the present invention, it is at least 25. (The left and right conditions may cause a part of the corrosion inhibitor to be detached, resulting in insufficient corrosion prevention effect. From a practical point of view, the lower pressure limit at the time of detachment is -15-200916573 O.OOlPa ° under the reduced pressure described above' In order to remove the corrosion inhibitor component of the present invention to a practically problem-free temperature (heat treatment temperature), it is loot ~ 300 ° C, preferably 120 ° C to 2 80 ° C, and 150 ° C to 250 ° C. It is better. When the temperature is less than 1 °C and completely detached, even if the condition of about 25 °C will cause some anti-uranium agent to be detached, the anti-corrosion effect will be insufficient. It must be greater than 300 °C. When it is detached, it may cause damage when it is detached from the process of the corrosion inhibitor. Further, the formation conditions or materials, the etch conditions, and the like of the respective layers applied in the wiring pattern forming process described above can be applied to previously known techniques. The material or the method for forming the diffusion preventing film of the film forming process can also be applied to a technique generally known in the prior art. Next, the present invention will be more specifically described by way of Examples and Comparative Examples. The present invention is not limited to the above embodiments. (Production of Semiconductor Element) A semiconductor element is produced as follows. First, as shown in Fig. 1, a tantalum carbide film is deposited on the conductive film 1 of the copper wiring in this order by a CVD method. 2 and the LoW-k film 3 of the interlayer insulating film. Then, the photoresist is coated and the photoresist is processed using the usual optical technique. The Low-k film 3 and the tantalum carbide film 2 are etched into a desired pattern by a dry etching technique. A through hole is formed, and a photoresist is removed by ashing to form a semiconductor element. The inner wall of the via hole of the manufactured semiconductor element is adhered to the etch residue 4. [Examples 1 to 20 and Comparative Example 1 2 0 ] -16- 200916573 The components shown in the following Tables 1 and 2 were mixed with the following detergent components to prepare the cleaning inhibitors of Examples 1 to 20 and Comparative Examples 1 to 20. The anticorrosive composition was washed to carry out the following evaluation {(washing agent component) mash: 0.4% by mass of ammonium fluoride, 0.03% by mass of glyoxylic acid, and remaining water B: 12% by mass of acetic acid, 15.2% by mass of ammonium acetate, 57.5 mass acetamide, 1 mass% ammonium fluoride, the remainder Water C liquid: 3.4% by mass of oxalic acid, 0.05% by mass of ascorbic acid, and remaining water D: 0.1% by mass of 1,2-diaminopropane, 0.5% by mass of fluorinated tetra-1. 5 mass% of acetic acid, and the remainder being water (evaluation 1 : Detergency) The semiconductor element shown in Fig. 1 was immersed in each of the cleaning inhibitors, immersed at 25 ° C for 2 minutes, and then rinsed with ultrapure water and dried. The surface condition was observed with an electron microscope (S-5500, manufactured by SEM HIGHTECHNOLOGIES Co., Ltd.), and the removal property of the etching residue, the corrosion of the copper wiring body, and the damage of Low were evaluated. (Evaluation 2: Corrosion resistance) In order to confirm the corrosion resistance of the corrosion inhibitor, a copper wafer-coated ruthenium wafer was immersed in each of the cleaning and etching compositions at 25 ° C, and then rinsed and dried using ultrapure water. . Subsequently, the ruthenium wafer was stained with ultrapure water obtained by melting carbon dioxide (the specific resistance was 0.2 Μ Ω corrosion inhibitor saturating group. Part of the dimethyl component was methylammonium, and the etch was used for drying. The detergency-k material is formed for 2 minutes at 25 ° C and immersed in -17 - 200916573 hereinafter referred to as carbonated water for 5 minutes. The copper surface obtained was observed by SEM to judge the corrosion of copper. It is believed that the corrosion inhibitor of copper corrosion is not functional. (Evaluation 3: Corrosion resistance) In order to confirm the ability of the corrosion inhibitor to suppress copper deterioration, a tantalum wafer formed by plating a copper film in its entirety was immersed in each cleaning anticorrosive composition at 25 ° C for 2 minutes, and then used. Rinse and dry with ultrapure water. Subsequently, it was allowed to stand in a clean room at 22 ° C and a humidity of 45 % for 3 days, and then the state of copper was measured using an X-ray photoelectron spectroscope (manufactured by XPS, VG Scientific). (Evaluation 4: easy-removability) In order to confirm the detachability (removability) from the copper surface of the corrosion inhibitor component, the following experiment was conducted. First, a tantalum wafer formed by plating a copper film in its entirety was immersed in the composition for cleaning and anti-corrosion shown in Tables 1 to 3 below at 25 ° C, and was observed for 2 minutes after the evaluation 2 was observed. Rinse and dry with ultrapure water. The copper film was heated at 200 ° C for 5 minutes under reduced pressure of 0.1 Pa. Subsequently, it was immersed in carbonated water at 25 ° C for 5 minutes and the copper surface was observed using SEM. In the evaluation 2, a composition for cleaning and anti-corrosion having an effect was observed, and a film for preventing corrosion by carbonated water was formed on the surface of the copper. When the protective film is removed from the copper surface by heating the copper film to which the protective film is adhered under reduced pressure, then when immersed in carbonated water, corrosion on the copper surface should be observed. Therefore, although it was not observed that the copper corrosion system was excellent when the SEM observation was used in the evaluation 2, when the SEM observation was used for the evaluation 4, it was observed that the copper corrosion system was good. -18-200916573 [Table 1] Examples Evaluation of cleaning agent corrosion inhibitor 1 Evaluation 2 Evaluation 3 Evaluation of 4 mm concentration of military halo % Corrosion of etch residue removal copper Damage of Low-k material 1 A 1,2,4-triazole 0.01 ◎ ◎ ◎ ◎ ◎ ◎ 2 B 1,2,4-triazole 0.01 ◎ ◎ ◎ ◎ ◎ 3 C 1,2,4-triazole 0.01 ◎ ◎ ◎ ◎ ◎ ◎ 4 A imine diacetic acid 1 ◎ ◎ ◎ ◎ ◎ ◎ 5 A 2二 disulfide 0.1 ◎ ◎ ◎ ◎ ◎ 6 D pyrazole 0.01 ◎ ◎ ◎ ◎ ◎ 〇 7 D 3,5-dimethylpyrazole 0.01 ◎ ◎ ◎ ◎ ◎ ◎ 8 B 3,5-dimethylpyrazole Oxazole dicarboxylic acid monohydrate 0.01 ◎ ◎ ◎ 〇〇 ◎ 9 D Hydroxyl ethylenediamine triacetic acid 0.01 ◎ ◎ ◎ 〇〇〇 10 A pyridin-1-carboxamidine hydrochloride 0.01 ◎ ◎ ◎ ◎ ◎ 〇 〇 11 B 3-Amino-5-hydroxypyrazole 0.01 ◎ ◎ ◎ ◎ ◎ 〇12 C 1-phenylpyrazole 0.01 ◎ ◎ ◎ ◎ 〇 13 D 3-Amino-4-phenylpyrazole 0.01 ◎ ◎ ◎ ◎ 〇 14 A 4-amino-3,5-dimethyl-1,2,4-triazole 0.01 ◎ ◎ ◎ ◎ ◎ 15 C Glycol ether diamine tetraacetic acid 0.01 〇〇〇〇〇〇 16 D hydroxyethyl iminodiacetic acid 0.01 〇〇 〇〇〇 A 17 A tri-extension ethylene tetraamine hexaacetic acid 0.01 ◎ ◎ ◎ 〇〇〇18 A EDTA dipropionate 0.01 ◎ ◎ ◎ ◎ ◎ 19 B Diisopropyl disulfide 0.01 ◎ ◎ ◎ ◎ ◎ ◎ 20 C Dibutyl disulfide 0.01 ◎ ◎ ◎ 〇〇〇-19- 200916573 [Table 2]

比 較 例 洗 淨 液 防蝕劑 評價1 評 價 2 評 價 3 評 價 4 種類 濃度 重量 % 蝕刻 殘渣 除去性 銅的 防蝕性 Low-k 材料的 損傷 1 A - - ◎ ◎ ◎ X X - 2 B - - ◎ ◎ ◎ X X - 3 C - - ◎ ◎ ◎ X X - 4 A 咪唑 1 X ◎ ◎ 〇 〇 X 5 B 菸鹼酸 0.1 ◎ 〇 〇 X X - 6 D - - ◎ ◎ ◎ X X - 7 B 苯并三唑 1 X ◎ ◎ ◎ X X 8 B 甘胺酸 0.01 ◎ ◎ ◎ X X - 9 C 1H-四唑 1 X ◎ ◎ 〇 X X 10 C 噻唑 1 〇 ◎ ◎ X X - 11 C 2-氫硫基-2-噻唑 琳 0.01 X ◎ ◎ ◎ X X 12 C 2-氫硫基-1-甲基 咪唑 0.01 X ◎ ◎ ◎ Δ X 13 A 4-胺基-3-氫硫基 -4H-1，2,4-三唑 0.01 X ◎ ◎ ◎ Δ X 14 C 聚丙烯酸 25000 0.1 ◎ ◎ ◎ X X - 15 c tr露糖 0.1 X X - 16 B 尿酸 0.01 Δ 〇 ◎ 〇 X X 17 D 腺嘌呤 0.1 Δ ◎ ◎ 〇 Δ X 18 D 四甲基胍 1 △ ◎ Δ X X - 19 C 2,2’聯二吡啶 0.1 X ◎ ◎ X X - 20 B 3-胺基-1，2,4-三唑 -5-羧羧 0.01 X ◎ ◎ ◎ Δ X 上述表中的各評價指標係如下所示。又，評價爲「◎」 及「〇」時，係實用上無問題的水準。 (評價1的蝕刻殘渣除去性） ◎:完全被除去。 〇：大致完全被除去。 △: 一部分殘留。 -20- 200916573 X :大部分殘留。 (評價1之銅的防蝕性） ◎:完全未認定有腐餘。 〇：幾乎未認定有腐蝕。 △:認定有凹陷狀或坑狀的腐蝕。 X :認定在銅層的全面有腐蝕並且認定銅層後退。 (評價1之L 〇 w - k材料的損傷） ◎:完全未認定形狀有變化。 〇：幾乎未認定形狀有變化。 △:認定有形狀有少許變化。 X :認定有形狀有大的變化。 (評價2) ◎:完全未認定有腐蝕。 〇·’幾乎未認定有腐蝕。 △:認定有凹陷狀或坑狀的腐蝕。 X :認定在銅層的全面有腐蝕並且認定銅層後退。 (評價3) ◎:完全未觀察到銅的變質物。 〇：幾乎未觀察到銅的變質物。 △:觀察到少許銅的變質物。 X :觀察到大量銅的變質物。 (評價4) ◎:認定在銅的全面有腐蝕。 〇：認定在銅的一部分有腐蝕。 -21 - 200916573 △:幾乎未認定銅有腐蝕。 X:完全未認定銅有腐蝕。 如表1所示，在實施例1〜2 0，不會損傷洗淨液（洗淨劑 成分）的性能，洗淨後之銅表面的保護效果亦優良且能夠藉 由減壓加熱而容易地除去。 【圖式簡單說明】 第1圖係模式性顯示乾式蝕刻後所形成鈾刻殘渣的狀 態之部分剖面圖。 【主要元件符號說明】 1 導電薄膜 2 碳化矽膜 3 L 〇 w - K 膜 4 蝕刻殘渣 -22-Comparative Example Cleaning Solution Corrosion Evaluation 1 Evaluation 2 Evaluation 3 Evaluation 4 Type Concentration Weight % Corrosion Resistance of Etch Removable Copper Corrosion of Low-k Material 1 A - - ◎ ◎ ◎ XX - 2 B - - ◎ ◎ ◎ XX - 3 C - - ◎ ◎ ◎ XX - 4 A Imidazole 1 X ◎ ◎ 〇〇X 5 B Nicotinic acid 0.1 ◎ 〇〇 XX - 6 D - - ◎ ◎ ◎ XX - 7 B benzotriazole 1 X ◎ ◎ ◎ XX 8 B glycine 0.01 ◎ ◎ ◎ XX - 9 C 1H-tetrazole 1 X ◎ ◎ 〇 XX 10 C thiazole 1 〇 ◎ ◎ XX - 11 C 2-Hydroxythio-2-thiazolene 0.01 X ◎ ◎ ◎ XX 12 C 2-Hydroxythio-1-methylimidazole 0.01 X ◎ ◎ ◎ Δ X 13 A 4-amino-3-hydrothio-4H-1,2,4-triazole 0.01 X ◎ ◎ ◎ Δ X 14 C Polyacrylic acid 25000 0.1 ◎ ◎ ◎ XX - 15 c Tr sugar 0.1 XX - 16 B uric acid 0.01 Δ 〇 ◎ 〇 XX 17 D Adenine 0.1 Δ ◎ ◎ 〇 Δ X 18 D Tetramethyl 胍 1 △ ◎ Δ XX - 19 C 2,2'bibipyridine 0.1 X ◎ ◎ XX - 20 B 3-amino-1,2,4-triazole-5-carboxycarboxyl 0.01 X ◎ ◎ Δ Δ X Each of the above tables Evaluation indicators are as Shown below. In addition, when it is evaluated as "◎" and "〇", it is a level that is practically problem-free. (Erosion residue removal property of evaluation 1) ◎: It was completely removed. 〇: It is almost completely removed. △: A part remains. -20- 200916573 X : Most of the residue. (Evaluation of copper corrosion resistance 1) ◎: No corrosion was found at all. 〇: Almost no corrosion has been identified. △: Corroded or pit-shaped corrosion was confirmed. X: It is assumed that the copper layer is completely corroded and the copper layer is receded. (Evaluation of L 〇 w - k material of evaluation 1) ◎: The shape was not changed at all. 〇: There is almost no change in shape. △: It is determined that there is a slight change in shape. X : I think there is a big change in shape. (Evaluation 2) ◎: Corrosion was not confirmed at all. 〇·’ Almost no corrosion has been identified. △: Corroded or pit-shaped corrosion was confirmed. X: It is assumed that the copper layer is completely corroded and the copper layer is receded. (Evaluation 3) ◎: No deterioration of copper was observed at all. 〇: Almost no copper metabolites were observed. △: A small amount of copper metamorphism was observed. X: A large amount of copper metamorphism was observed. (Evaluation 4) ◎: It is confirmed that there is corrosion in the whole of copper. 〇: It is determined that there is corrosion in a part of copper. -21 - 200916573 △: There is almost no corrosion of copper. X: Copper is not considered to be corroded at all. As shown in Table 1, in Examples 1 to 20, the performance of the cleaning liquid (cleaner component) was not impaired, and the protective effect of the copper surface after washing was also excellent, and it was easy to heat by decompression. Remove. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a partial cross-sectional view showing the state of the uranium residue formed after dry etching. [Main component symbol description] 1 Conductive film 2 Tantalum carbide film 3 L 〇 w - K film 4 Etching residue -22-

Claims (1)

200916573 十、申請專利範圍： 1 · 一種洗淨防蝕用組成物’其係使用於具有含銅金屬配線 之半導體元件或顯示元件等的製程，含有防蝕劑成分及 洗淨劑成分， §亥防触劑成分係選自由Π比哩、3，5 -二甲基Π比哩、3，5 - Π比哩 二羧酸一水合物、吡唑-1-甲脒鹽酸鹽、3-胺基-5 _羥基啦 口坐、1 -苯基耻卩坐、3 -胺基-4 -苯基卩比哩、1，2，4 -三哩、4 -胺 ... 基-3，5 -二甲基-1，2，4 -三唑、亞胺基二乙酸、羥基伸乙二 胺三乙酸、乙二醇醚二胺四乙酸、羥乙基亞胺基二乙酸、 二伸乙四胺六乙酸、伸乙二胺二丙酸鹽酸鹽、二異丙基 二硫醚、二丁基二硫醚及二乙基二硫醚所組成群組之至 少1種，而 該洗淨劑成分係選自由氟化錢、氟化四甲截、乙酸錢、 乙酸、乙醛酸、草酸、抗壞血酸、1,2 -二胺基丙烷及二甲 基乙醯胺所組成群組之至少1種。 , 2_如申請專利範圍第1項之洗淨防蝕用組成物，其中該防 i 蝕劑成分的濃度爲0.001 ~5質量％，且該洗淨劑成分的濃 度爲0.01〜90質量％。 3·—種半導體元件或顯示元件之製法，包含以下製程： 配線圖案形成製程，其係在基板上依照順序形成作爲導 電用配線使用之含銅的導電薄膜及用以進行配線間的絕 緣之層間絕緣膜，並在該表面塗布光阻劑來形成感光層 且對其施行選擇性曝光及顯像處理來形成光阻圖案，並 且以該光阻圖案作爲遮罩而施行蝕刻處理後，藉由灰化 -23- 200916573 除去光阻劑來形成配線圖案； 洗淨處理製程，其係藉由洗淨處理來除去蝕刻處理後的 蝕刻殘渣； 加熱處理製程，其係在該洗淨處理製程後施行加熱處 理：及 防止擴散膜形成製程，其係在藉由該加熱處理而露出的 配線圖案表面形成防止擴散膜； 該洗淨處理製程之洗淨處理係使用如申請專利範圍第！ 項之洗淨防蝕用組成物，且 該加熱處理製程之加熱處理的條件係壓力爲 0.001 〜600Pa、溫度爲 100°C~300 °C。 -24-200916573 X. Patent application scope: 1 · A cleaning and anti-corrosion composition' is used in a process of a semiconductor element or a display element having copper-containing metal wiring, containing a corrosion inhibitor component and a detergent component, § The agent component is selected from the group consisting of ruthenium iridium, 3,5-dimethyl ruthenium ruthenium, 3,5-deuterium ruthenium dicarboxylic acid monohydrate, pyrazole-1-carboxamidine hydrochloride, 3-amino group- 5 _ hydroxy sputum sitting, 1-phenyl sputum sitting, 3-amino-4-phenylindole oxime, 1,2,4-trisyl, 4-amine...yl-3,5-di Methyl-1,2,4-triazole, iminodiacetic acid, hydroxyethylenediaminetriacetic acid, glycol ether diaminetetraacetic acid, hydroxyethyliminodiacetic acid, diethylenetetramine At least one of the group consisting of acetic acid, ethylenediamine dipropionate, diisopropyl disulfide, dibutyl disulfide, and diethyl disulfide, and the detergent component is At least one selected from the group consisting of fluorinated money, fluorinated tetramethyl acetate, acetic acid, acetic acid, glyoxylic acid, oxalic acid, ascorbic acid, 1,2-diaminopropane, and dimethylacetamide is selected. The cleaning anticorrosive composition according to the first aspect of the invention, wherein the concentration of the anticorrosive component is 0.001 to 5% by mass, and the concentration of the detergent component is 0.01 to 90% by mass. 3. A method of fabricating a semiconductor device or a display device, comprising the following process: a wiring pattern forming process for forming a copper-containing conductive film used as a conductive wiring on a substrate in sequence and an interlayer for insulating between wirings An insulating film is coated on the surface to form a photosensitive layer and subjected to selective exposure and development processing to form a photoresist pattern, and after the etching process is performed as a mask by the photoresist pattern, by ash -23-200916573 removing the photoresist to form a wiring pattern; the cleaning process is performed by removing the etching residue after the etching process by a cleaning process; the heat treatment process is performed after the cleaning process Processing: and a diffusion preventing film forming process for forming a diffusion preventing film on the surface of the wiring pattern exposed by the heat treatment; the cleaning process of the cleaning process is used as in the patent application scope! The composition for cleaning and anti-corrosion of the item, and the heat treatment condition of the heat treatment process is a pressure of 0.001 to 600 Pa and a temperature of 100 to 300 °C. -twenty four-
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US8802608B2 (en) 2014-08-12
CN101755324B (en) 2011-10-12
KR20100044777A (en) 2010-04-30
WO2009013987A1 (en) 2009-01-29
JP5278319B2 (en) 2013-09-04
CN101755324A (en) 2010-06-23
JPWO2009013987A1 (en) 2010-09-30

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